The present invention relates to a composition for the oxidation dyeing of keratin fibres and in particular of human keratin fibres, comprising at least one specific para-phenylenediamine which is substituted in the 2-position on the benzene ring, and at least one cationic or amphoteric substantive polymer. The invention also relates to the use of such a composition in cosmetic applications.
It is known to dye keratin fibres, and in particular human hair, with dye compositions containing oxidation dye precursors, in particular ortho- or para-phenylenediamines, ortho- or para-aminophenols, generally referred to as xe2x80x9coxidation basesxe2x80x9d, and couplers, also referred to as coloration modifiers, more particularly meta-phenylenediamine, metaminophenols and meta-diphenols, which allow the xe2x80x9cfoundationxe2x80x9d colorations obtained with the products of condensation of the oxidation bases to be modified and enriched with glints.
It is thus especially known to dye hair with dye compositions which contain, as oxidation dye precursors, para-phenylenediamine of the type 1-hydroxyalkyl-2,5-diaminobenzene or alternatively of the type 1-hydroxyalkoxy-2,5-diaminobenzene, these precursors being combined, if required, with one or more common couplers. Such compositions are described, for example, in WO Patent Application 80/00214 and in European Patent EP-B-0,400,330, the disclosures of which are incorporated herein by reference.
However, it appeared to the Inventors that, in order to be even more satisfactory, the above dyes needed to be less selective, that is to say that they needed to be less sensitive, in dyeing terms, to the various degrees of sensitization of the hair to be dyed, in order for the colour range observed on this more or less sensitized hair to be as narrow as possible, and thus in order for the hair to be dyed uniformly. It furthermore appeared important for these compositions to be able to generate dyes whose power, on the one hand, and whose simultaneous resistance to atmospheric agents (light, bad weather), to perspiration and to the various cosmetic treatments to which the hair may be subjected (washing, permanent-waving and the like), on the other hand, is further enhanced.
Now, after considerable research conducted in this matter, it has been discovered that it is possible to obtain oxidation dyes based on compounds of the 1-hydroxyalkyl- or 1-hydroxyalkoxy-2,5-diaminobenzene type, these dyes exhibiting a markedly enhanced selectivity compared with those known hitherto, when a cationic or amphoteric substantive polymer is combined with the above compounds.
It has also been discovered that the dyes obtained using these novel compositions are more intense, while at the same time remaining very resistant to atmospheric agents and to the various above mentioned cosmetic treatments.
These discoveries form the basis of the present invention. The subject of the present invention is thus an oxidation dye composition for keratin fibres, in particular for human keratin fibres such as hair, comprising, in a medium appropriate for dyeing, at least one oxidation dye precursor (oxidation base), and if required, at least one coupler, and at least one cationic or amphoteric substantive coupler; the at least one oxidation dye precursor being selected from para-phenylenediamines of formula (I): 
in which m is an integer equal to zero or 1, and n is an integer ranging from 1 to 4, or an acid addition salt thereof.
According to the invention, the oxidation dye precursors of formula (I) above are preferably used in combination with one or more couplers.
The new dyes obtained in the context of the present invention make it possible to achieve intense, fast and uniform colorations from the root to the tip of the hairs.
Another subject of the present invention concerns a ready-to-use composition for dyeing keratin fibres, in particular human keratin fibres such as hair, which contains at least one para-phenylenediamine of formula (I) above, at least one cationic or amphoteric substantive polymer, one or more optional couplers and at least one oxidizing agent.
The invention is also aimed at a process for dyeing keratin fibres, and in particular human keratin fibres such as hair, comprising the steps of: (i) applying to the fibres the dye composition (A1), which comprises, in a medium appropriate for dyeing, at least one para-phenylenediamine of formula (I), as described above, as an oxidation dye precursor, and one or more optional couplers, in combination with at least one cationic or amphoteric substantive polymer; and (ii) using an oxidizing agent, the oxidizing agent being applied to the fibres simultaneously with or subsequently to the dye composition, to develop the colour of the dye composition in an acidic, neutral or alkaline medium. In accordance with this embodiment of the present invention, the oxidizing agent can be mixed with the dye composition (A1) at the time of application of the dye composition to the fibres, or can be separately contained in a composition (B1) that is separately applied to the fibres simultaneously with the dye composition, or is separately applied to the fibres subsequently to the application of the dye composition.
The invention is also aimed at a variant of this process, which comprises the steps of: (i) applying to the fibres a dye composition (A2), which comprises, in a medium appropriate for dyeing, at least one para-phenylenediamine of formula (I), as described above; and (ii) applying an oxidizing composition (B2), which comprises an oxidizing agent and at least one cationic or amphoteric substantive polymer, to the fibres simultaneously with or subsequently to the dye composition, to develop the colour of the dye composition in an alkaline, neutral or acidic medium. In accordance with this embodiment of the present invention, the dye composition may further comprise at least one coupler and/or a cationic or amphoteric substantive polymer. Also in accordance with this embodiment of the present invention, the oxidizing composition (B2) can be added to the dye composition (A2) at the time of the application of the dye composition to the fibres or can be separately applied to the fibres simultaneously with or subsequently to the dye composition.
A further subject of the present invention is multi-compartment dyeing devices or xe2x80x9ckitsxe2x80x9d, a first compartment of which contains a dye composition comprising at least one para-phenylenediamine of formula (I), as described above, as an oxidation dye precursor, one or more optional couplers and at least one cationic or amphoteric substantive polymer, and a second compartment of which contains an oxidizing agent.
According to another variant, a further subject of the invention is multi-compartment dyeing devices or xe2x80x9ckitsxe2x80x9d, a first compartment of which contains a dye composition comprising at least one para-phenylenediamine of formula (I), as described above, as an oxidation dye precursor, and one or more optional couplers, in the presence or absence of a cationic or amphoteric substantive polymer, and a second compartment of which contains an oxidizing composition which comprises an oxidizing agent and at least one cationic or amphoteric substantive polymer.
However, other characteristics, aspects, objectives and advantages of the invention will emerge even more clearly upon reading the description and the examples which follow.
The para-phenylenediamine acid salts of formula (I) which may be used according to the invention are preferably chosen from the hydrochlorides, the sulphates, the hydrobromides and the tartrates.
Among the oxidation dye precursors of formula (I) which may be used in the context of the present invention, it is preferred to use 2-(xcex2-hydroxyethyl)-para-phenylenediamine and 2-(xcex2-hydroxyethyloxy)-para-phenylenediamine.
The concentration of this (these) precursor(s) or of the salts thereof may preferably range approximately from 0.05 to 10% by weight relative to the total weight of the dye composition applied to the hair, and more preferably range approximately from 0.1 to 5% by weight.
As defined herein, the cationic or amphoteric substantive polymer refers to a polymer with the ability to be deposited on keratin fibres, in particular human keratin fibres such as hair, as determined conventionally using the test described by Richard J. Crawford, Journal of the Society of Cosmetic Chemists, 1980, 31-(5), pages 273 to 278 (development by Red 80 acidic dye), the disclosure of which is incorporated herein by reference.
These cationic or amphoteric substantive polymers may be chosen from those previously described in the literature, in particular in European Patent Application EP-A-0,557,203, from page 4 line 19 to page 12 line 14, the disclosure of which is incorporated herein by reference.
Other quaternized cellulose ether derivatives may also be mentioned, such as those described in European Application EP-A-0,189,935, the disclosure of which is incorporated herein by reference, and in particular the polymer marketed under the name xe2x80x9cQuatrisoft LM 200xe2x80x9d by the Union Carbide company; these polymers are also defined in the CTFA dictionary (5th edition, 1993) as hydroxyethylcellulose quaternary ammoniums which have been reacted with an epoxide substituted with a lauryl-dimethylammonium group and are listed therein under the name xe2x80x9cPolyquaternium 24xe2x80x9d.
It is also possible to mention the products referred to in the CTFA dictionary (5th edition, 1993) as xe2x80x9cPolyquaternium 37xe2x80x9d, xe2x80x9cPolyquaternium 32xe2x80x9d, and xe2x80x9cPolyquaternium 35xe2x80x9d, which correspond respectively, as regards xe2x80x9cPolyquaternium 37xe2x80x9d, to crosslinked poly(methacryloyloxyethyltrimethylammonium chloride), as a 50% dispersion in mineral oil, sold under the name Salcare SC95 by the Allied Colloids company; as regards xe2x80x9cPolyquaternium 32xe2x80x9d, to the crosslinked copolymer of acrylamide and methacryloyloxyethyltrimethylammonium chloride (20/80 by weight), as a 50% dispersion in mineral oil, sold under the name Salcare SC92 by the Allied Colloids company, and; as regards xe2x80x9cPolyquaternium 35xe2x80x9d, to the methosulphate of the copolymer of methacryloyoxyethyl trimethylammonium and methacryloyloxyethyldimethylacetylammonium, sold under the name Plex 7525L by the Rohm GmbH company.
Among the cationic or amphoteric substantive polymers which may be used according to the invention, it is especially preferred to use:
dimethyldiallylammonium chloride homopolymer, sold under the name xe2x80x9cMerquat 100xe2x80x9d by the Merck company;
the copolymers of dimethyldiallylammonium chloride and acrylamide, sold under the names xe2x80x9cMerquat 550xe2x80x9d and xe2x80x9cMerquat Sxe2x80x9d by the Merck company;
the quaternary polyammonium polymers prepared and described in French Patent 2,270,846, the disclosure of which is incorporated herein by reference, consisting of repeating units corresponding to the following formula (II): 
xe2x80x83and the molecular weight of which, determined by gel permeation chromatography, ranges from 9,500 to 9,900;
the quaternary polyammonium polymers prepared and described in French Patent 2,270,846, the disclosure of which is incorporated herein by reference, consisting of repeating units corresponding to the following formula (III): 
xe2x80x83and the molecular weight of which, determined by gel permeation chromatography, is 1,200xc2x110%, i.e., approximately ranges from 1080 to 1320;
the quaternary polyammonium polymers described and prepared in U.S. Pat. Nos. 4,157,388, 4,390,689, 4,702,906 and 4,719,282, the disclosures of which are incorporated herein by reference, and consisting of repeating units corresponding to the following formula (IV): 
xe2x80x83in which p represents an integer ranging approximately from 1 to 6; D may be nonexistent or may represent a group xe2x80x94(CH2)rxe2x80x94COxe2x80x94 in which r represents a number equal to 4 or to 7, the molecular weight, determined by gel permeation chromatography, of these polymers preferably being less than 100,000, and more preferably being less than or equal to 50,000; such polymers are sold in particular by the Miranol company under the names xe2x80x9cMirapol A15xe2x80x9d, xe2x80x9cMirapol AD1xe2x80x9d, xe2x80x9cMirapol AZ1xe2x80x9d and xe2x80x9cMirapol 175xe2x80x9d;
the copolymer of diallyldimethylammonium chloride and acrylic acid (80/20), sold under the name Merquat 280 by the Calgon company.
The concentration of the cationic or amphoteric substantive polymer may preferably range approximately from 0.02 to 10% by weight relative to the total weight of the dye composition applied to the hair, and more preferably ranges from 0.05 to 5% by weight.
The oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, and persalts such as perborates and persulphates. It is particularly preferred to use hydrogen peroxide.
The composition (A), which contains the combination of the dyes as described above, preferably has a pH which ranges from 3 to 11, and which may be adjusted to the desired value using basifying agents usually used in the dyeing of keratin fibres. Typical basifying agents include aqueous ammonia, alkali metal carbonates, alkanolamines, for example mono-, di- and triethanolamines as well as derivatives thereof, sodium hydroxide or potassium hydroxide, the compounds of formula: 
in which R is a propylene residue which is optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; R1, R2, R3 and R4 simultaneously or independently of each other, represent a hydrogen atom, a C1-C4 alkyl radical or C1-C4 hydroxyalkyl radical. Standard acidifying agents may also be used to adjust the pH. Typical acidifying agents include inorganic or organic acids such as, for example, hydrochloric acid, tartaric acid, citric acid and phosphoric acid.
The pH of the composition (B) containing the oxidizing agent as defined above is such that, after mixing with the composition (A), the pH of the composition applied to the human keratin fibres preferably ranges from 3 to 11. The pH can be adjusted to the desired value using acidifying agents or optionally using basifying agents which are well known in the state of the art, such as those described above.
The oxidizing composition (B) preferably consists of aqueous hydrogen peroxide solution.
According to a preferred embodiment of the dyeing process of the invention, the dye composition (A) described above is mixed, at the time of use, with an oxidizing solution in a sufficient amount to develop a coloration. The mixture obtained is then applied to the human keratin fibres and is preferably left in place for 5 to 40 minutes, and more preferably for 15 to 30 minutes, after which the fibres are rinsed, washed with shampoo, rinsed again and dried.
As indicated above, the preferred dye compositions according to the invention also contain, besides the oxidation dye precursors defined above, one or more couplers.
Among these couplers, there may preferably be mentioned: 5-amino-2-methylphenol, 5-N-(xcex2-hydroxyethyl)amino-2-methyl-phenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(B-hydroxyethyloxy)benzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diamino-phenoxy)propane, sesamol, xcex1-naphthol, 6-hydroxyindole and 4-hydroxyindole. It is also possible to use other common couplers.
In addition to the oxidation dye precursors defined above and the optional combined couplers, the dye compositions may also contain other oxidation dye precursors as well as direct dyes, in order especially to modify the shades or to enrich the shades with glints. Their concentration by weight may preferably range approximately from 0.0005 to 10%, and may more preferably range approximately from 0.001 to 5%, relative to the total weight of the dye composition applied to the hair.
Among the additional oxidation dye precursors which may be used in the context of the present invention, there may preferably be mentioned: 4-aminophenol, 4-amino-2-methyl-phenol, 4-amino-3-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-3-hydroxymethylphenol, para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-(xcex2-hydroxyethyloxy)-para-phenylenediamine, 1-N-bis(xcex2-hydroxy-ethyl)amino-4-aminobenzene and 1-(xcex2-methoxyethyl)amino-4-aminobenzene.
The direct dyes themselves may be chosen from nitro dyes, azo dyes or anthraquinone dyes.
The dye compositions may also contain antioxidants. These may be chosen in particular from sodium sulphite, thioglycolic acid, thiolactic acid, sodium bisulphite, dehydroascorbic acid, hydroquinone, 2-methylhydroquinone, tert-butylhydroquinone and homogentisic acid, and they may preferably be present in proportions ranging approximately from 0.05 to 1.5% by weight relative to the total weight of the composition.
In their preferred embodiments, the dye compositions according to the invention also contain surface-active agents which are well known in the art, in proportions approximately ranging from 0.5 to 55% by weight, and preferably from 2 to 50% by weight, relative to the total weight of the composition. Organic solvents in proportions approximately ranging from 1 to 40% by weight, and preferably from 5 to 30% by weight, relative to the total weight of the composition may also be included in the dye compositions according to the invention. The dye compositions of the invention may also contain any other cosmetically acceptable adjuvant which is known in the prior art in the oxidation dyeing of hair.
The composition applied to the hair may be provided in various forms, such as in the form of a liquid, a cream, a gel or any other form which is suitable for dyeing keratin fibres and in particular human hair. In particular, the compositions of the invention may be packaged under pressure in an aerosol can in the presence of a propellent and may form a foam.
Concrete examples illustrating the invention will now be given.
In these examples, the dyeing selectivity criterion was evaluated using the colour variation index I which was calculated according to the Nickerson equation below (see in this regard xe2x80x9cJournal of the Optical Society of Americaxe2x80x9d, 1944, Sept., Vol. 34, No. 9, pp. 550-570), the disclosure of which is incorporated herein by reference:
xe2x80x83I=0.4Coxcex94H+6xcex94V+3xcex94C
in which the parameters H, V and C represent the parameters of the Munsell notation (ASTM Standard D 1535-68) which defines the colour (H denoting the shade or Hue, V denoting the intensity or Value, and Co denoting the purity or Chromaticity of the lock relative to which it is desired to evaluate the variation in colour).